WO2005123246A1 - Dispositif de radiation normale, filtre l'utilisant, filtre c)ramique optiquement assist) - Google Patents

Dispositif de radiation normale, filtre l'utilisant, filtre c)ramique optiquement assist) Download PDF

Info

Publication number
WO2005123246A1
WO2005123246A1 PCT/JP2005/009790 JP2005009790W WO2005123246A1 WO 2005123246 A1 WO2005123246 A1 WO 2005123246A1 JP 2005009790 W JP2005009790 W JP 2005009790W WO 2005123246 A1 WO2005123246 A1 WO 2005123246A1
Authority
WO
WIPO (PCT)
Prior art keywords
light
emitting device
ceramic filter
photocatalyst
group
Prior art date
Application number
PCT/JP2005/009790
Other languages
English (en)
Japanese (ja)
Inventor
Chihiro Kawai
Ryuichi Inoue
Original Assignee
Sumitomo Electric Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Electric Industries, Ltd. filed Critical Sumitomo Electric Industries, Ltd.
Priority to EP05743654.5A priority Critical patent/EP1772187A4/fr
Priority to CA002570352A priority patent/CA2570352A1/fr
Priority to JP2006514680A priority patent/JP4743634B2/ja
Priority to US11/628,947 priority patent/US7767158B2/en
Publication of WO2005123246A1 publication Critical patent/WO2005123246A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M29/00—Scaring or repelling devices, e.g. bird-scaring apparatus
    • A01M29/12—Scaring or repelling devices, e.g. bird-scaring apparatus using odoriferous substances, e.g. aromas, pheromones or chemical agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
    • A61L9/18—Radiation
    • A61L9/20—Ultraviolet radiation
    • A61L9/205—Ultraviolet radiation using a photocatalyst or photosensitiser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
    • B01D39/083—Filter cloth, i.e. woven, knitted or interlaced material of organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2027—Metallic material
    • B01D39/2051—Metallic foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2068—Other inorganic materials, e.g. ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/88—Handling or mounting catalysts
    • B01D53/885—Devices in general for catalytic purification of waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/062—Tubular membrane modules with membranes on a surface of a support tube
    • B01D63/065—Tubular membrane modules with membranes on a surface of a support tube on the outer surface thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/066—Tubular membrane modules with a porous block having membrane coated passages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/123—Ultraviolet light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/045—Deodorising additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0471—Surface coating material
    • B01D2239/0478—Surface coating material on a layer of the filter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/065—More than one layer present in the filtering material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/1216—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/802—Photocatalytic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/34—Energy carriers
    • B01D2313/345—Electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0282—Dynamic pores-stimuli responsive membranes, e.g. thermoresponsive or pH-responsive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0875—Gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0877—Liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0892—Materials to be treated involving catalytically active material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Definitions

  • the present invention relates to a surface-emitting device using a surface-emitting device having a function of emitting visible light or ultraviolet light to excite a photocatalyst to decompose or sterilize harmful substances, and a filtration filter using the same. And a light-assisted ceramic filter.
  • photocatalysts such as air purifiers
  • photocatalysts such as TiO
  • the photocatalyst is excited by irradiating ultraviolet light radiated from a mercury lamp or the like onto a porous material carrying a functional material.
  • a mercury lamp or the like since a mercury lamp or the like must be installed separately, for example, in the case of an air purifier, the entire device size becomes large.
  • Patent Document 1 a method of exciting a photocatalyst by using a surface light emitter as a light source has been proposed (see Patent Document 1).
  • This excites a photocatalyst using an inorganic EL light emitting sheet that emits short wavelength visible light to ultraviolet light as a light source.
  • an inorganic EL light emitting sheet that emits short wavelength visible light to ultraviolet light as a light source.
  • two sheets are stacked, and harmful components in the fluid present between them are decomposed and removed by photocatalysis. But with this structure
  • a commonly used ceramic filter has a lotus-like cross section in which a plurality of flow paths are formed perpendicular to the cross section, and a filtration layer is formed on the inner wall of the flow path.
  • the permeation performance should be improved by reducing the thickness of the filtration layer with a small pore diameter required for actual filtration. Designed to. In other words, it has a structure that is a filter layer for performing filtration and a support body that supports the filter layer. Ceramic filters with a cross-sectional diameter of about 30 mm and a length of about 500 to 1000 mm are often used.
  • the overall porosity is about 35 to 40%, the pore size of the filtration layer is about 0.005 to 1 / ⁇ , the pore size of the intermediate layer and the support is 2 to 3 / ⁇ , and 10 to 20 respectively. / ⁇ ⁇ .
  • the total thickness of the filtration layer and the intermediate layer is about one hundred and several tens / zm.
  • Such a ceramic filter can only perform physical filtration based on the relationship between the size of the trapped material and the pore size.
  • the luminous body and the electrode itself have a porous structure, and when the fluid permeates the luminous body and the electrode itself, the porous body itself radiates ultraviolet rays, and the photocatalyst supported in the porous body becomes an organic substance.
  • a ceramic filter having a function of decomposing bacteria or sterilizing bacteria and viruses see Patent Document 2.
  • the luminous body is obtained by slightly sintering the semiconductor particles.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2003-200043
  • Patent Document 2 International Publication No. 04Z006969 pamphlet
  • the present invention can efficiently cause a catalytic reaction without using an external ultraviolet light source such as an ultraviolet lamp or an ultraviolet LED. It is an object of the present invention to provide a surface emitting device capable of causing a catalytic reaction well. Further, it is another object of the present invention to provide a surface emitting device that can easily perform insulation treatment of a light emitting layer, does not require advanced technology, and can be obtained at low cost.
  • Another object of the present invention is to provide a ceramic filter which can be easily manufactured at low cost and has a function of decomposing organic substances or sterilizing bacteria, viruses and the like.
  • the inventor has invented a surface emitting device and a ceramic filter having a unique structure. That is, the present invention comprises the following configurations (1) to (31).
  • a surface emitting device having a function of emitting visible light or ultraviolet light by electoran luminescence, and a plurality of through holes serving as a fluid flow path are formed in a direction perpendicular to the surface of the surface light emitter.
  • a surface emitting device comprising:
  • the light emitting layer of the surface light emitter is sandwiched between members that reflect visible light and Z or ultraviolet light.
  • the phosphor power used in the inorganic EL device The general formula is Zn A S: Cu, D (
  • A is at least one group 2A element selected from the group consisting of Be, Mg, Ca, Sr and Ba
  • D is at least one type selected from group 3B or 7B elements, and 0 ⁇ ⁇
  • the phosphor used in the inorganic EL device has a general formula of Zn A S: Ag, D (
  • A is at least one group 2A element selected from the group consisting of Be, Mg, Ca, Sr and Ba
  • D is at least one type selected from group 3B or 7B elements, and 0 ⁇ ⁇
  • a light-assisted ceramic filter characterized by comprising a ceramic filter having a plurality of flow paths, a photocatalyst layer disposed on a side surface thereof, and a surface light emitting body.
  • the phosphor used for the inorganic EL the general formula is Zn A S: Ag, D (A in the formula
  • the surface light emitting device of the present invention is a surface light emitting device that can excite a photocatalyst with a surface light emitter that emits visible light or ultraviolet light.
  • a catalytic reaction can be efficiently caused without using an external ultraviolet light source such as an ultraviolet lamp or an ultraviolet LED.
  • an external ultraviolet light source such as an ultraviolet lamp or an ultraviolet LED.
  • it cannot be processed with an external light source! / It absorbs ultraviolet light so strongly that even if it is a polluted fluid, a catalytic reaction can occur efficiently.
  • the surface light emitter since the surface light emitter has a plurality of through-holes serving as a flow path of a fluid, light is emitted without any special cost that prevents the fluid from passing through the light emitting layer. Layer insulation treatment can be performed.
  • the catalytic reaction vessel using the surface emitting device of the present invention is capable of decomposing organic substances and sterilizing bacteria and the like, so that NOx, SOx, CO gas, diesel particulates, pollen, and pollutants, which are pollutants in the air, can be obtained.
  • Decomposition and removal of dust, mites, etc. Decomposition and removal of organic compounds contained in sewage, Sterilization light source for general bacteria and viruses, Decomposition of harmful gases generated in chemical plants, Decomposition of odor components, Ultrapure water production equipment Germicidal light source in various fields. It can also be applied to automobile exhaust gas treatment honeycomb materials, air purifier filters for air conditioners, sewage filtration filters, various water purifiers, sterilization of hot springs, and insect repellents.
  • the photo-assisted ceramic filter of the present invention ordinary filtration based on physical size and smaller organic substances and bacteria such as viruses that cannot be collected by filtration can be performed by the photocatalytic function. Can be disassembled. Further, the optically assisted ceramic filter of the present invention can be easily manufactured at low cost.
  • FIG. 1 is a diagram showing an example of the structure of the surface emitting device of the present invention.
  • (A) is a side view
  • (b) is a perspective view.
  • FIG. 2 is a view showing another example of the structure of the surface emitting device of the present invention.
  • FIG. 3 is a diagram showing an example of the structure of an inorganic EL device used in the present invention.
  • FIG. 4 is a view showing another structural example of the inorganic EL device used in the present invention.
  • FIG. 5 is a view showing another example of the structure of the surface emitting device of the present invention.
  • FIG. 6 is a diagram showing a structural example of a light-assisted ceramic filter of the present invention.
  • FIG. 7 is a diagram showing a manufacturing process of the surface emitting device in the example.
  • FIG. 8 is an explanatory diagram of a method for evaluating a surface-emitting device according to an example.
  • FIG. 9 is an explanatory diagram of a method for evaluating a surface emitting device of a comparative example.
  • One of the basic structures of the surface emitting device of the present invention is a surface emitting body having a function of emitting visible light or ultraviolet light, and a porous layer having a photocatalyst formed on the upper surface and the Z or lower surface thereof. And a plurality of through-holes, which are fluid flow paths, are formed in a direction perpendicular to the surface of the surface light emitter.
  • a surface light emitter having a function of emitting visible light or ultraviolet light a light emitting sheet called an electoran luminescence (EL) sheet is preferably used.
  • EL electoran luminescence
  • FIG. 1 shows an example (first structure) of a specific structure of the surface emitting device of the present invention.
  • (a) is a side view
  • (b) is a perspective view.
  • a porous layer having a photocatalyst is arranged on the upper surface and the lower surface of a surface light emitter in which a plurality of strip-shaped light emitting layers are arranged at a fixed gap.
  • the fluid to be processed flows in from the surface of one porous layer, passes through the gap of the surface light emitter, and is discharged through the porous layer on the opposite side.
  • Visible light or ultraviolet light emitted from the surface light emitter is applied to the surface of the porous layer directly above and below the surface light emitter. Can spread uniformly over the entire porous material layer to excite the photocatalyst.
  • the fluid that has passed through the porous layer on one surface passes through the gap between the surface light emitters and is finally discharged as a clarified fluid through the porous layer on the other surface.
  • the porous body having the photocatalyst is not uniformly irradiated with light or the brightness is reduced.
  • the flow path area ratio is preferably 30% to 70% of the whole.
  • the surface light emitter is electrically disconnected from the outside except for the electrode portion. Preferably they are rimmed. By doing so, the device can be used for any highly conductive liquid.
  • the cross section in which the through hole is formed is also electrically insulated.
  • a method for sealing the cross section once an EL sheet with a through hole is formed, a liquid resin is poured into the through hole and dried, and then, while maintaining electrical insulation, the resin is applied to the resin again. There is also a method such as forming a through hole.
  • the fluid does not pass through the light emitting layer (thereby forming a plurality of through holes serving as a fluid flow path), so that the insulating treatment is performed without any special cost. Can be. Further, since the through holes are opened, there is an advantage that heat generated during light emission can be quickly discharged through the through holes.
  • the second structure of the surface emitting device of the present invention is a structure in which light emitting layers are arranged in a lattice as shown in FIG.
  • the cost is basically reduced to one set of lead wires. Effective for reduction.
  • the lattice structure is a preferable structure because light is more uniformly guided into the porous body.
  • the size of the grid serving as the flow path is preferably 5 mm or less.
  • the shape of the flow path is not limited, and may be square or circular.
  • light emitted from the light emitting layer can be concentrated in the flow channel by controlling the structure of the surface light emitter.
  • the upper and lower surfaces of the light-emitting layer are sandwiched between members such as a metal material that reflects visible light and ultraviolet light, the light from the light-emitting layer is repeatedly reflected by these members and confined. After being concentrated on the flow path through the cross section of the light emitting layer (surface on the flow path side) without being released to the upper and lower surfaces, the flow path is also released to the outside. That is, with such a structure, a device in which only the flow path emits light can be obtained.
  • Such a structure can be easily achieved by, for example, using an electrode of an inorganic EL device used as a surface light emitter made of a metal material that reflects visible light or ultraviolet light and reflects it.
  • the photocatalyst that is in direct contact with the cross section of the light emitting layer in the flow channel is irradiated with visible light or ultraviolet light without interposing a space.
  • Photocatalyst has the following issues. In other words, when the photocatalyst is placed in a highly contaminated state, there is a problem in that the contaminants adhere thickly to the photocatalyst surface, the light from the external light source cannot reach the photocatalyst, and the photocatalytic function stops.
  • the visible light or ultraviolet light intervenes in the photocatalyst directly in contact with the cross section of the light emitting layer of the flow channel. This problem can be solved because the irradiation will continue without irradiation.
  • the porous body having a photocatalyst filled in the flow path may be a porous body carrying a photocatalyst or a porous body filled with a particulate photocatalyst.
  • the filter can function as a filtration filter having the same bactericidal action as a normal mercury lamp without a photocatalyst.
  • the first structure of electoran luminescence used in the present invention is generally called a dispersion type EL, and a light emitting layer is formed by dispersing a phosphor having a function of emitting visible light or ultraviolet light in a dielectric. Consists of a structure.
  • the second structure is called a thin-film EL, which has a structural strength in which a thin-film light-emitting layer with a thickness of 1 m or less is sandwiched between insulating layers.
  • the light-emitting layer contains no resin and consists only of phosphor. It is composed.
  • Thin-film EL has the characteristic that it emits a large amount of light because of its high emission luminance and has high efficiency to excite the photocatalyst. It has low luminous efficiency of 1 lmZW or less and consumes large power. In addition, there are disadvantages such as the necessity of an expensive gas phase synthesis apparatus. On the other hand, the dispersion type EL has the advantages of low luminance, but the luminous efficiency may exceed 10 lmZW, low power consumption, and the use of a powder coating process, resulting in significantly lower manufacturing costs.
  • an inorganic EL device is preferable because of its ability to use an organic EL device or an inorganic EL device, and excellent durability such as UV resistance.
  • an inorganic EL device has a light emitting layer structure in which phosphor particles such as ZnS are dispersed in a dielectric resin, and a structure in which high dielectric constant ceramics such as BaTiO are dispersed in the dielectric resin.
  • a light emitting layer has a structure in which an insulating layer is a main structure, a light emitting layer has a structure in which an insulating layer is interposed, and an electrode is formed on the insulating layer.
  • FIG. 3 shows a structural example of the inorganic EL device used in the present invention.
  • FIG. 3 (a) has an insulating layer only on the lower surface of the light emitting layer
  • FIG. 3 (b) has an insulating layer on the upper and lower surfaces of the light emitting layer.
  • both the front and back electrodes can be formed of a transparent conductive film. That is, when a porous layer having a photocatalyst that emits light by ultraviolet light is disposed on the upper and lower surfaces of the surface light emitter, both the front and rear electrodes are formed of a transparent conductive film.
  • the resin base material and the protective layer resin are transparent to light having a wavelength emitted by the surface light emitter, and have electrical insulation properties.
  • the resin transmits ultraviolet light and becomes ⁇ .
  • Polyethylene terephthalate (PET) resin which is generally used, is difficult to transmit ultraviolet light having a wavelength of 360 nm or less. Therefore, when the emission wavelength is shorter than this, it is preferable to use an ultraviolet transparent resin.
  • the ultraviolet transmitting resin include Atarilite manufactured by Mitsubishi Rayon.
  • the shorter the emission wavelength the more easily the resin deteriorates. In this case, there is an advantage that all the constituent members can be made of an inorganic material without using a resin.
  • the transparent conductive film As the front and back electrodes (see FIG. 4), light from the light emitting layer is emitted by these electrodes.
  • the light is repeatedly confined, becomes confined, is not emitted to the upper and lower surfaces, passes through the cross section of the light-emitting layer, concentrates on the flow path, and then is also released to the outside.
  • the protective layer resin on the front and back sides does not need to have a light-transmitting property with respect to light having a wavelength emitted by the surface light emitter, but at least the protective layer resin on the cross-sectional side needs to have a light-transmitting property.
  • electricity It has insulating properties.
  • the type of phosphor used for electora luminescence is not limited.
  • the following phosphors can be used.
  • the emission wavelength of the surface light emitter has a peak wavelength at 540 nm or less, a visible light responsive photocatalyst can be excited.
  • a visible light responsive photocatalyst can be excited.
  • ZnS doped with Cu, Cl, A1, or the like is preferable because of its high luminous efficiency.
  • These phosphors emit blue to green light with a peak wavelength around 450 to 540 nm and can excite a visible light responsive photocatalyst, but light with a peak wavelength below 460 nm can efficiently excite the photocatalyst. It is preferable because it can be excited.
  • the general formula is Zn A S: Cu, D (A in the formula is a group of Be, Mg, Ca, Sr and Ba.
  • At least one element selected from Group 2A and D is at least one element selected from Group 3B or Group 7B, and 0 ⁇ ⁇ 1), and has a blue-Cu type emission function Those containing a phosphor can also be preferably used.
  • D include Al, Ga, Cl, and F.
  • Al and C1 are preferable in terms of raw material costs.
  • X is preferably 0.25 ⁇ x ⁇ 0.6.
  • Blue-Cu emission is described below.
  • a ZnS: Cu, C1 phosphor doped Cu replaces the position of Zn while C1 replaces the position of S. Since the emission wavelength is green at around 530 nm, it is called Green-Cu emission.
  • Green-Cu emission if Cu enters the gap of the crystal lattice of ZnS at the same time as substituting for the Zn position, a short-wavelength luminescence at around 460 nm called Blue-Cu emission occurs.
  • a part of the added Cu remains as highly conductive Cu S inside the phosphor, and this phosphor
  • EL emission occurs due to concentration or other reasons.
  • the emission wavelength of this light emission depends on the band gap of the semiconductor that is the base of the phosphor, and the larger the band gap, the shorter the wavelength of light emission. Therefore, if blue-Cu type light emission is used, for example, ZnS: Cu, CI, Al (450-460 nm) or ZnMgS: Cu, CI, Al (410-430 nm) can be used.
  • the phosphor is particularly preferably an ultraviolet light-emitting phosphor having a peak wavelength of light of less than 400 nm, more preferably in the range of 300 to 375 nm.
  • the anatase TiO photocatalyst having the highest photocatalytic performance can be excited.
  • a phosphor that emits ultraviolet light ZnS doped with Ag, Cl, and A1 is a candidate.
  • a semiconductor having ZnS as a first main component and a second component having or not including a Group VI compound semiconductor MgS, CaS, SrS, BeS, BaS, etc.
  • MgS, CaS, SrS, BeS, BaS, etc. has an axceptor level.
  • the general formula is ZnA S: Ag, D (where A is a group of Be, Mg, Ca, Sr and Ba
  • At least one element selected from Group 2A and D is at least one element selected from Group 3B or Group 7B, and 0 ⁇ ⁇ 1), and has a blue-Cu type emission function Phosphors can also be used preferably.
  • D include Al, Ga, Cl, F and the like.
  • X 0.25 ⁇ x ⁇ 0.6 force is preferable.
  • the light emission mechanism of this phosphor is exactly the same as that of ZnS: Cu, C1, and even when Ag is doped, it is called Blue-Cu light emission.
  • ZnS: Ag, CI, Al (399 nm) or ZnMgS: Ag, CI, Al (369 nm) can be used.
  • Ag S is formed in the same manner as above, but since the conductivity is low, electric field concentration does not occur.
  • EL emission can be achieved by combining other conductive materials.
  • Other candidate materials include ZnF: Gd, which has an emission line spectrum of 31 lnm.
  • the threshold voltage can be reduced.
  • an emission wavelength of 350 nm or less is preferable because the photocatalyst can be most efficiently excited.
  • resin ceramics is used for the dielectric. In the case of a device that emits visible light with an emission wavelength exceeding 360 nm, the same resin used in ordinary EL devices cannot be used.
  • the dielectric resin include cyanoresin (manufactured by Shin-Etsu Danigaku). However, for shorter wavelengths, if a dielectric resin is used for a long period of time, the resin may deteriorate, so it is preferable to use a dielectric ceramic instead of the resin.
  • dielectric ceramics various materials such as BaTiO, SrTiO, and PbTiO having a high dielectric constant can be considered.
  • a dielectric ceramic dispersed in a resin or a dielectric ceramic alone is used as the insulating layer.
  • the emission peak wavelength of the surface light emitter is 540 nm or less, a visible light responsive photocatalyst can be excited.
  • TiO: S, TiO: N, etc. are preferred as the visible light compatible photocatalyst
  • the photocatalytic performance is the highest!
  • the anatase TiO 2 photocatalyst can be excited.
  • the photocatalyst is mainly composed of anatase TiO
  • any material may be used as long as it has a through-hole, but a foamed metal, a foamed ceramic, a resin woven cloth, or the like is preferable. These materials have high porosity and excellent permeability. A photocatalyst may be supported on these materials. In order to uniformly guide light into a porous body having a photocatalyst, a porous body having a high refractive index and a material strength is more preferable. For example, there is a method in which the titanium oxide itself having a high refractive index is made into a porous body.
  • the pore diameter of the porous layer and the porous body is small because reflection is repeated inside the porous body.
  • the average pore size is 500 m or less.
  • the pore diameter of the porous body can be measured with a mercury porosimeter or the like. There is no particular lower limit on the pore diameter, but as the pore diameter decreases, the permeation resistance of the fluid increases, so the standard is about 0.005 m.
  • the photocatalyst is carried on the porous body by a sol-gel method or the like, the larger the specific surface area of the porous body is, the higher the photocatalytic effect is, which is preferable.
  • the surface light emitting device of the present invention can be used as a filtration filter, and the filtration filter is emptied.
  • the thinner the whole device the better.
  • the thickness of the EL sheet is 1 mm or less, and the thickness of the porous layer having a catalytic function.
  • the total sum of the EL sheet and the porous body supporting the photocatalyst is 3 mm or less.
  • a ceramic filter can be used as the porous layer.
  • Fig. 5 shows a specific example of the structure when a ceramic filter is used as the porous layer.
  • FIG. 5A is a perspective view
  • FIG. 5B is a cross-sectional view of a plane parallel to the flow direction of the stock solution.
  • the basic structure is a ceramic filter that mainly purifies the liquid by cross-flow filtration, and a through hole in which the flow path of the ceramic filter and the flow path of the surface light emitter communicate with each other, and preferably have the same cross-sectional shape as the ceramic filter.
  • the surface luminous body sheet having the following is laminated.
  • the photocatalyst is formed as a photocatalyst layer on the inner wall of the flow path of the ceramic filter.
  • the light emitted from the light emitting layer can be concentrated in the channel by controlling the structure of the surface light emitter.
  • the light applied to the flow channel spreads throughout the flow channel while repeatedly absorbing and reflecting on the inner wall of the flow channel, ie, the photocatalytic layer formed on the surface of the filtration layer, and sequentially excites the photocatalyst.
  • the method of concentrating light emitted from the light emitting layer of the surface light emitter in the flow path is, when an inorganic EL sheet is used, the upper and lower surfaces of the light emitting layer (the surface on which the ceramic filter is provided).
  • the light is sandwiched between members such as metal materials that do not transmit or absorb visible light or ultraviolet light, the light of the luminous layer is repeatedly reflected by these members, and is confined. It is concentrated in the flow path without passing out through the cross section of the light emitting layer (surface on the flow path side).
  • Inorganic EL devices can be easily manufactured by using upper and lower electrodes made of a metal material such as aluminum or gold.
  • the method for forming the photocatalyst layer is, for example, a method in which a liquid in which titanium oxide particles are dispersed is filtered through the present ceramic filter to form a deposited layer of titanium oxide particles on the surface of the filtration layer. May be heated and fired so as to be appropriately sintered. Alternatively, the viscosity of the titanium alkoxide solution to be transferred to the titanium oxide after firing may be adjusted, filtered in the same manner, and then fired.
  • the filtration layer of the ceramic filter may be formed of titanium oxide.
  • the photocatalyst is supported on a support that is not located on the inner wall of the flow channel, no force is applied.
  • the electrode is made of indium tin oxide (ITO) or ZnO, etc. so that the light is emitted in the vertical direction of the surface light emitter without being focused on the flow path. What is necessary is just to use a transparent conductive film.
  • the supporting method of the photocatalyst can be formed by immersing the support in a liquid in which the viscosity of a titanium alkoxide solution to be converted after firing to titanium oxide is adjusted, pulling the support up, and then firing.
  • the surface light emitting device of the present invention has a laminated structure in which a surface light emitting body and a porous layer are repeatedly laminated.
  • the surface emitting device of the present invention When the surface emitting device of the present invention is used as a filtration filter, for example, relatively large particles such as particles floating in the air are physically collected on the surface of a porous body having a photocatalyst, and small particles are used as a photocatalyst. It is decomposed by the photocatalyst in the process of passing through the inside of the porous body. Therefore, as the laminated structure of the surface light emitter and the porous material layer is repeated, there is a drawback that the force that becomes a filter having high reliability is reduced, whereas the transmission performance is reduced.
  • the light-assisted ceramic filter of the present invention is a ceramic filter that mainly purifies liquid by cross-flow filtration.
  • Cross-flow filtration refers to a form of filtration in which a permeate is recovered in a direction perpendicular to the flow of the stock while circulating the stock.
  • FIG. 6 shows one specific example of the first structure of the optically assisted ceramic filter of the present invention.
  • the basic structure consists of a ceramic filter whose flow path is perpendicular to the cross section, a surface emitting sheet, and a photocatalytic sheet (photocatalytic layer).
  • the ceramic filter is composed of a filtration layer for filtration, an intermediate layer, and a support.
  • the photocatalyst sheet is wound on the side of the ceramic filter according to the cross-sectional shape of the ceramic filter. Further, a surface light emitter sheet is wound on the surface.
  • the section of the ceramic filter refers to a section perpendicular to the flow direction of the undiluted solution, and the side faces refer to surfaces other than the bottom surface of the cylindrical ceramic filter.
  • the clarified fluid that has passed through the filtration layer is discharged to the side of the ceramic filter, and is impregnated into the photocatalyst sheet.
  • the light emitted from the surface illuminator excites the photocatalyst in the photocatalyst sheet to develop a photocatalytic effect. Decompose or sterilize bacteria, viruses, etc.
  • the fluid after the decomposition and sterilization treatment is collected from the end of the ceramic filter along the in-plane direction inside the photocatalyst sheet.
  • the fluid that has been disassembled and sterilized will Since it can be discharged to the outside through a plurality of through-holes, the collection amount can be increased as compared with the case where there is no through-hole.
  • the surface light emitting device having a through hole according to the present invention can be used as the surface light emitting sheet having a through hole.
  • the photocatalyst sheet a sheet in which a photocatalyst powder is supported on a surface of a porous resin or metal or ceramic, or a sheet in which a photocatalyst film is coated is used.
  • the photocatalyst may be coated on the side of the ceramic filter.
  • titanium oxide is generally used. Therefore, the emission wavelength of the surface light emitter needs to be in a wavelength band that can excite the photocatalyst.
  • a visible light responsive photocatalyst light having a peak wavelength of 460 nm or less is preferable. Above 460 nm, photocatalytic performance may be manifested, but performance is reduced.
  • an anatase-type titanium oxide which is an ultraviolet-responsive photocatalyst
  • light having a peak wavelength of 400 nm or less is preferable. In general, the UV-responsive photocatalyst performs better.
  • Dispersion-type inorganic EL is a material in which a phosphor is dispersed in a dielectric resin and a light-emitting layer is formed on a resin substrate sheet by screen printing or a doctor blade.
  • Inorganic EL is preferred because it is resistant to moisture. Although it is difficult for organic EL to emit ultraviolet light, visible light has the advantage that it is easier to obtain one with higher brightness than inorganic EL. Organic EL is sensitive to moisture Therefore, when used in water, there is a problem that the life is short.
  • an organic EL or inorganic EL device can be used as the surface light emitter.
  • an inorganic EL having excellent durability such as ultraviolet resistance is preferable.
  • an inorganic EL surface light emitter is composed of a light emitting layer having a structure in which phosphor particles such as ZnS are dispersed in a dielectric resin and a high dielectric constant ceramic such as BaTiO.
  • the main structure is composed of an insulating layer dispersed in a resin, and electrodes are formed on the insulating layer.
  • the emission wavelength is ultraviolet light
  • the degradation of the resin is apt to progress.
  • the resin is not used and all the constituent members can be made of an inorganic material.
  • resin degradation often occurs mainly with ultraviolet light having a wavelength of 350 nm or less, so if no ultraviolet light in this range is contained, resin may be used.
  • light emitted from the light emitting layer can be concentrated on the photocatalyst sheet side.
  • a structure in which light is emitted only to the inside (light emitting layer side) can be achieved by using a metal material such as aluminum or gold for the electrode facing the outside.
  • the same phosphor as the phosphor used in the above surface light emitting device can be used.
  • the light-assisted ceramic filter of the present invention mainly purifies liquids by cross-flow filtration, but may filter gas.
  • Cross-flow filtration refers to a form of filtration that recovers a permeate in a direction perpendicular to the flow of the stock solution while circulating the stock solution.
  • the use of the photo-assist type ceramic filter of the present invention makes it possible to decompose or sterilize powerful bacteria, organic substances, and the like, which cannot be collected only by physical filtration, by photocatalysis.
  • a transparent resin sheet (product name: Acrylite S, product number # 000, manufactured by Mitsubishi Rayon) having a size of 100 ⁇ 100 mm and a thickness of 100 m was prepared.
  • This sheet contains grid-shaped holes of various sizes in advance. Were opened at 4 mm intervals (pitch).
  • BaTiO Average particle size 0.2 ⁇
  • a SiC porous body having a size of 120 ⁇ 120 mm, a thickness of 0.1 mm, and various average pore diameters shown in Table 1 and a porosity of 50% was used.
  • TiO S average particle size 0.03 m
  • the doping amount of S was set to 2 at% with respect to oxygen.
  • the protective layer resin (FIG. 7 (a)) was coated with aluminum by a sputtering method in a grid shape having a line width of 50 ⁇ m and a thickness of 0: m, and the electrode lead wires were bonded. (Fig. 7 (b))
  • a resin prepared by dispersing and dissolving a resin (cyanoresin) in cyclohexanone so as to be 25 vol% was prepared.
  • the phosphor powder was dispersed in this solution in Ar gas (25 vo 1%) to prepare a slurry.
  • a coating layer having a thickness of 60 / zm was formed on the inner insulating layer surface by screen printing. (Fig. 7 (e))
  • the transparent conductive film was coated on the surface of the light emitting layer in the same manner as the electrode 1, and the electrode lead wire was bonded. (Fig. 7 (f))
  • Sheets having the same shape as the protective layer resin used in (1) were laminated and thermocompression bonded to completely seal. (FIG. 7 (g)) Thereafter, epoxy resin was applied to the cross section of the through hole.
  • the porous SiC body supporting the photocatalyst was arranged on the upper and lower surfaces of the surface light emitting sheet, and the ends were screwed to obtain a filtration filter.
  • the filtration filter using the surface emitting device of the present invention has a shorter solution time than the external light source method. This is considered to be because light emitted by the external light source method is easily absorbed by liquids having high turbidity, so that the surface of the porous TiO2 material cannot be excited by force.
  • the emitted The decomposition time is short because the catalyst functions uniformly throughout the entire body while repeating scattering inside the porous layer.
  • a transparent resin sheet (product name: Acrylite S, product number # 000, manufactured by Mitsubishi Rayon) having a size of 100 ⁇ 100 mm and a thickness of 100 m was prepared.
  • lattice-shaped holes each having a side of lmm were previously formed at lmm intervals.
  • BaTiO average particle size 0.2 ⁇
  • ZnS Ag, Cl powder Average particle size 3 m Emission peak wavelength: 380 nm (ultraviolet) ZnS—20 mol% MgS: Ag, C1 powder
  • Example (1) a surface-emitting device was manufactured according to Example (1).
  • the protective layer resin was coated with aluminum in a thickness of 0: m by sputtering, and the electrode leads were bonded.
  • the above resin (Shin-Etsu Chemical Co., Ltd. (Cyanoresin)) was dispersed and dissolved in cyclohexanone so as to be 25 vol%, and then BaTiO powder was dispersed (25 vol%).
  • a resin was prepared by dispersing and dissolving a resin (cyanoresin) in cyclohexanone at 25 vol%.
  • a slurry was prepared by dispersing the above phosphor powder in this solution in Ar gas (25 vol%).
  • a coating layer having a thickness of 60 m was formed on the inner insulating layer surface by screen printing.
  • the surface of the light emitting layer was coated with aluminum, and the electrode lead wires were bonded.
  • Sheets having the same shape as the protective layer resin used in (1) were laminated and thermocompression bonded to completely seal.
  • the photocatalyst particles were formed into a lmm-diameter and 300-m-thick porous body by dry pressing to obtain a porous body with a porosity of 65%. This was loaded into a hole (flow path) using a resin adhesive and fixed.
  • Formaldehyde was dispersed in the air to produce 3.
  • the obtained contaminated air and the filtration filter prepared above were installed in the same manner as in Example (1).
  • photocatalyst particles were formed into a diameter of 100 mm and a thickness of 300 ⁇ m by dry pressing to produce a porous sheet having a porosity of 65%.
  • the same photocatalytic reaction experiment was performed while irradiating an ultraviolet LED lamp with an emission wavelength of 360 nm and an output of 5 mW at a distance of 50 mm above and below the photocatalyst sheet.
  • the filtration time of the filter of the present invention was shorter than when the LED was used. This is because light from an external light source cannot efficiently excite the photocatalyst, which is easily reflected on the photocatalyst sheet surface. And light attenuation due to the separation of the light source.
  • the filtration filter using the surface emitting device of the present invention has a problem in that light concentrates in the hole, comes into contact with the photocatalyst filled with the light source, and because the light source and the photocatalyst come extremely close to each other. Since there is almost no attenuation, the decomposition efficiency is considered to be high.
  • the filtration filter of the present invention does not require an external light source, it requires only a small installation space as a thin filter.
  • a filtration filter was prepared in the same manner as in Example (2) except that the flow path was not filled with the photocatalyst, and the following porous layers were laminated.
  • a fluororesin porous membrane (porosity: 95%) having a size of 100 ⁇ 100 mm and a thickness of 100 ⁇ m was prepared. (photocatalyst)
  • Toluene was dispersed in air to prepare 3.0 L of contaminated air having a concentration of 500 ppm.
  • the obtained contaminated air and the filtration filter prepared above were installed in a device as shown in Fig. 8. While the obtained contaminated air was circulated at a flow rate of 0.3 LZmin, various voltages and frequencies shown in Table 3 were applied between the electrodes. Was applied. Measure the time until the toluene concentration reaches zero.
  • the filtration filter of the present invention does not require an external light source, it requires only a small installation space as a thin filter.
  • a multi-layer (three-layer) filter with 37 holes of 3 mm diameter in a cross section of 30 mm diameter, length of 500 mm, porosity was 35%. This filter was able to separate 100% of particles having a particle size of 0.2 / zm. 16 pieces of this ceramic filter cut to a length of 30 mm were prepared
  • a sol manufactured by Sumitomo Chemical
  • a raw material liquid of anatase type titanium oxide powder average particle size: 60 nm, manufactured by Tika
  • BaTiO average particle size 0.2 ⁇
  • ZnS Ag, CI powder average particle size 3 ⁇ m
  • MgS Ag, CI powder average particle size 3 ⁇ m
  • ZnS Ag, Cl, ZnS-20mol% MgS: Ag, CI, those obtained by coating the surfaces of these phosphors with CuS were used.
  • the resin sheet was coated with an A1 electrode film by a thickness of 0.4 m by a sputtering method, and an electrode lead wire was bonded to the A1 film.
  • the resin was dispersed and dissolved in cyclohexanone so as to be 25 vol%, and then BaTi 2 O powder was dispersed (25 vol%) to prepare a slurry.
  • a coating layer having a thickness of 30 ⁇ m was formed.
  • a solution prepared by dispersing and dissolving a resin in cyclohexanone at 25 vol% was prepared.
  • a slurry was prepared by dispersing the phosphor powder in this solution in Ar gas (25 vol%).
  • a coating layer having a thickness of 60 m was formed on the surface of the insulating layer by screen printing.
  • an electrode lead wire was bonded to the A1 electrode film.
  • the A1 electrode side of this sheet and the light-emitting layer were overlapped, thermocompression-bonded at 120 ° C., and sealed to obtain a surface-emitting sheet.
  • the EL sheets prepared in this manner were punched in the same size and structure as the cross section of the ceramic filter of (1), and 17 sheets were prepared.
  • Perforated EL sheets were alternately stacked on the cross-section of a 30 mm long ceramic filter to produce a laminated ceramic filter with a length of about 480 mm.
  • Mouth was added with ethylene and adjusted to lppm.
  • the filter was set in a cross-flow filtration device, and filtration was performed with a transmembrane pressure difference of lkgZcm 2 while applying an alternating electric field of 500 V and 5 kHz between the electrodes of the EL sheet. The test was also performed when no electric field was applied using only the ceramic filter.
  • the alumina particle concentration after filtration was measured with an absorptiometer.
  • the concentration of trichlorethylene (TCE) after filtration was analyzed by gas chromatography.
  • the area of the photocatalyst is larger than that of the ceramic filter in which the photocatalyst sheet and the surface light emitter are wound, so that the decomposition efficiency of TCE is increased.
  • a multi-layer (three-layer) filter with 37 holes of 3 mm diameter in a cross section of 30 mm diameter, length of 500 mm, porosity was 35%. This filter was able to separate 100% of particles having a particle size of 0.2 / zm.
  • a polyethylene sheet having a width of 95 mm and a length of 500 mm and a porosity of 90% was prepared. After being immersed in a sol (manufactured by Sumitomo Chemical) containing visible light responsive titanium oxide powder (average particle size: 60 nm) or a sol containing anatase type oxidized titanium powder (average particle size: 60 nm), pulled up, After drying at room temperature for 24 hours, the photocatalyst was coated on the resin surface.
  • a sol manufactured by Sumitomo Chemical
  • BaTiO average particle size 0.2 ⁇
  • the resin sheet was coated with an A1 electrode film by a thickness of 0.4 m by a sputtering method, and an electrode lead wire was bonded to the A1 film.
  • the resin was dispersed and dissolved in cyclohexanone so as to be 25 vol%, and then BaTi 2 O powder was dispersed (25 vol%) to prepare a slurry.
  • a coating layer having a thickness of 30 ⁇ m was formed.
  • a solution prepared by dispersing and dissolving a resin in cyclohexanone at 25 vol% was prepared.
  • a slurry was prepared by dispersing the phosphor powder in this solution in Ar gas (25 vol%).
  • a coating layer having a thickness of 60 m was formed on the surface of the insulating layer by screen printing.
  • the electrode lead wire was bonded to the ITO electrode film.
  • the ITO electrode side of this sheet and the light-emitting layer were overlapped and sealed by thermocompression bonding at 120 ° C. to obtain a surface light-emitting sheet.
  • a photocatalyst sheet was wrapped around the ceramic filter side, and a surface illuminant was further wrapped over it.
  • the alumina particle concentration after filtration was measured with an absorptiometer.
  • the concentration of trichlorethylene (TCE) after filtration was analyzed by gas chromatography.
  • the UV emission EL sheet showed high decomposition performance. This is because the performance of the anatase photocatalyst is higher than that of the visible light responsive type, so even if the luminescence intensity (sum of the visible light intensity and the ultraviolet intensity) of the EL sheet itself is low, relatively high photocatalytic performance was developed. Conceivable.
  • the surface emitting device of the present invention can also be used as a filtration filter.
  • the particles and the like floating in the fluid those larger than the pore diameter of the porous body having a catalytic function are collected. Since the surface emitting device of the present invention can have an extremely thin structure, it is highly effective when used as a filter for air cleaning among various uses.
  • the air conditioner when the air conditioner is installed at an air intake port of an air conditioner or the like, the air conditioner can be provided with an air purifying function.
  • the surface emitting device of the present invention has a high heat release function since the through-holes are opened, the surface luminous body hardly deteriorates due to heat even when a high voltage or a high frequency is applied to emit light. There is a feature.
  • the surface emitting device of the present invention can be used for display applications while allowing gas such as air to pass therethrough. Also in this case, heat generation can be prevented, so that the display has a long service life.
  • the surface emitting device of the present invention is capable of decomposing and removing NOx, SOx, CO gas, diesel particulates, pollen, dust, mites and the like, which are pollutants in the atmosphere, and removing organic compounds contained in sewage. It can be applied to various fields such as decomposition and removal, sterilization of general bacteria and viruses, decomposition of harmful gas generated in chemical plants, decomposition of odorous components, and the like. In addition, as a product type, it can be applied to all filters in the above fields, and it can be used for air purification, sewage filtration, various water purifiers, insect repellents, etc. Is also applicable.
  • Light sources for backlights in EL displays, mobile phones, etc., light sources for fixing toner used in digital photo printers for digital cameras, light sources for curing UV-curable resins, and light sources for disinfecting medical catheters carrying photocatalysts Can be used for When combined with a phosphor that emits visible light, it emits an AC electric field during the day and can be used as a display or filter that emits light at night without power.
  • a phosphor that emits visible light
  • it emits an AC electric field during the day and can be used as a display or filter that emits light at night without power.
  • insects prefer to gather in ultraviolet rays having a wavelength around 365 nm, they can be used as a sheet-like insect collecting panel, which is effective for malaria prevention and the like.
  • the photo-assisted ceramic filter of the present invention can excite a photocatalyst with a surface light emitter that emits visible light or ultraviolet light, and has a function of decomposing organic substances or sterilizing bacteria, viruses, and the like. It is.
  • a catalytic reaction without using an external ultraviolet light source such as an ultraviolet lamp or an ultraviolet LED.
  • the catalyst reaction can be efficiently caused even in a liquid having a low degree of transparency, which absorbs ultraviolet rays which cannot be processed by an external light source.
  • the light-assisted ceramic filter of the present invention is generally used for liquids, but can also exert its function for gases.
  • gases such as NOx and SOx
  • dust and diesel particulates can be collected by the filtration function, and NOx gas, etc. can be decomposed by the photocatalytic function.
  • decomposition and removal of pollen, dust, mites, etc. decomposition and removal of organic compounds contained in sewage, sterilization of general bacteria and viruses, decomposition of harmful gases generated in chemical plants, decomposition of odor components, etc. It can be applied to various fields.
  • a product type it can be applied to all filters in the above fields, and can be applied to air purification, sewage filtration, various water purifiers, insect repellents, etc.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Toxicology (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Geology (AREA)
  • Public Health (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Biomedical Technology (AREA)
  • Veterinary Medicine (AREA)
  • Textile Engineering (AREA)
  • Birds (AREA)
  • Insects & Arthropods (AREA)
  • Pest Control & Pesticides (AREA)
  • Electromagnetism (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Catalysts (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Arrangement Of Elements, Cooling, Sealing, Or The Like Of Lighting Devices (AREA)
  • Electroluminescent Light Sources (AREA)
  • Filtering Materials (AREA)
  • Physical Water Treatments (AREA)

Abstract

Ce dispositif de radiation normale est capable d'entraîner efficacement une réaction de catalyseur, même dans un fluide contaminé absorbant violemment les rayons ultraviolets qui ne peuvent pas être traités par une source lumineuse externe ou sans utiliser de source lumineuse de rayons ultraviolets externe comme une lampe ultraviolette et une LED ultraviolette. De plus, est présenté un filtre céramique qui peut être facilement fabriqué à faible coût et comprend un catalyseur optique capable de dissoudre les objets organiques ou de stériliser les bactéries et les virus. Ce dispositif de radiation normale comprend un corps de radiation normale ayant une fonction d'émission de rayons visibles ou de rayons ultraviolets par électroluminescence ; ici, plusieurs orifices sont formés dans la direction verticale relativement au plan du corps de radiation normale, de manière à servir de parcours pour le fluide. De plus, un filtre céramique optiquement assisté comprend un filtre céramique ayant plusieurs parcours du flux et une couche de catalyseur optique ainsi qu'un corps de radiation normale qui sont agencés sur la surface latérale du filtre céramique. SCH)MA: FIG. 1: A COUCHE POREUSE PORTEUSE DU CATALYSEUR OPTIQUE B COUCHE D')MISSION DE LUMI(RE C COUCHE D'ISOLATION D )LECTRODE E CORPS DE RADIATION NORMALE F PARCOURS DU FLUX
PCT/JP2005/009790 2004-06-15 2005-05-27 Dispositif de radiation normale, filtre l'utilisant, filtre c)ramique optiquement assist) WO2005123246A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP05743654.5A EP1772187A4 (fr) 2004-06-15 2005-05-27 Dispositif de radiation normale, filtre l'utilisant, filtre ceramique optiquement assiste
CA002570352A CA2570352A1 (fr) 2004-06-15 2005-05-27 Dispositif de radiation normale, filtre l'utilisant, filtre c)ramique optiquement assist)
JP2006514680A JP4743634B2 (ja) 2004-06-15 2005-05-27 面発光デバイス
US11/628,947 US7767158B2 (en) 2004-06-15 2005-05-27 Surface light-emitting device, filtering device using same, and optically assisted ceramic filter

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2004-176881 2004-06-15
JP2004176881 2004-06-15
JP2004-352306 2004-12-06
JP2004352306 2004-12-06

Publications (1)

Publication Number Publication Date
WO2005123246A1 true WO2005123246A1 (fr) 2005-12-29

Family

ID=35509490

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/009790 WO2005123246A1 (fr) 2004-06-15 2005-05-27 Dispositif de radiation normale, filtre l'utilisant, filtre c)ramique optiquement assist)

Country Status (6)

Country Link
US (1) US7767158B2 (fr)
EP (1) EP1772187A4 (fr)
JP (1) JP4743634B2 (fr)
CA (1) CA2570352A1 (fr)
TW (1) TW200613045A (fr)
WO (1) WO2005123246A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007217480A (ja) * 2006-02-15 2007-08-30 Sumitomo Electric Ind Ltd 蛍光体、その製造方法及び該蛍光体を含んだ無機ｅｌ素子
JP2009540557A (ja) * 2006-06-07 2009-11-19 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ 光デバイス及び光デバイスを製造する方法
JP2012018798A (ja) * 2010-07-07 2012-01-26 Sharp Corp 面発光素子および浄化装置
JP5022525B1 (ja) * 2011-05-11 2012-09-12 パイオニア株式会社 照明装置
JP2012238575A (ja) * 2012-03-13 2012-12-06 Pioneer Electronic Corp 照明装置
JP2013244440A (ja) * 2012-05-24 2013-12-09 Sharp Corp 水浄化装置
JP2016080347A (ja) * 2014-10-14 2016-05-16 ネプチューン−ベンソン，エルエルシー マルチセグメント型管板
JP2017029923A (ja) * 2015-07-31 2017-02-09 株式会社 シリコンプラス ウイルス除去用フィルター
JP2017221896A (ja) * 2016-06-15 2017-12-21 東芝ライテック株式会社 光触媒装置

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5090227B2 (ja) * 2008-03-26 2012-12-05 学校法人金沢工業大学 有機エレクトロルミネッセンス素子、照明装置および表示装置
KR101717518B1 (ko) * 2009-09-07 2017-03-17 엘지전자 주식회사 공기조화기
EP2526572B1 (fr) * 2010-01-19 2019-08-14 LG Innotek Co., Ltd. Boîtier et son procédé de fabrication
US8585980B2 (en) 2010-09-07 2013-11-19 Puradigm, Llc Enhanced photo-catalytic cells
US8585979B2 (en) * 2010-09-07 2013-11-19 Puradigm, Llc Enhanced photo-catalytic cells
US9101904B2 (en) 2012-05-25 2015-08-11 Honeywell International Inc. Air purification system using ultraviolet light emitting diodes and photocatalyst-coated supports
KR101822891B1 (ko) * 2013-02-12 2018-01-29 엘지전자 주식회사 냉장고 및 그 금속 광촉매 필터 제조 방법
US10471170B2 (en) * 2015-06-29 2019-11-12 Puresys Co., Ltd. Air purifying sterilizer module with improved catalytic performance and air purifying sterilizer including the same
US10207936B2 (en) 2016-02-19 2019-02-19 Silanna UV Technologies Pte Ltd Ultraviolet reactor with planar light source
KR102477412B1 (ko) * 2016-07-22 2022-12-15 엘지전자 주식회사 자외선 살균모듈 및 이를 구비한 공기조화기
KR102414268B1 (ko) 2016-07-22 2022-06-29 엘지전자 주식회사 공기조화기
KR102393890B1 (ko) 2016-07-22 2022-05-03 엘지전자 주식회사 공기조화기
KR20180010877A (ko) * 2016-07-22 2018-01-31 엘지전자 주식회사 자외선 살균 모듈 및 이를 포함하는 공기조화기
CN107129021A (zh) * 2017-06-30 2017-09-05 陈雪飞 一种绿色环保阳光天然净化器
US20190263518A1 (en) * 2018-02-28 2019-08-29 Espen Garner Unmanned Aerial Vehicle Having an Insect Trap
US11022361B2 (en) 2018-08-29 2021-06-01 Whirlpool Corporation Air filtration system for antimicrobial refrigerators
CN114269690A (zh) 2019-07-31 2022-04-01 捷通国际有限公司 水处理系统
CH717554A2 (fr) * 2020-06-19 2021-12-30 Admajora Sa Élément filtrant pour la purification et la désinfection de l'air et de l'eau.

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003200043A (ja) * 2002-01-04 2003-07-15 Tasuke Iwashita 有機ｅｌ素子または無機ｅｌ素子を用いた有機物質分解装置
WO2004006969A1 (fr) * 2002-07-11 2004-01-22 Sumitomo Electric Industries, Ltd. Semiconducteur poreux et procede de production correspondant
JP2004024461A (ja) * 2002-06-25 2004-01-29 Denso Corp 空気浄化装置

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2582868Y2 (ja) * 1992-10-23 1998-10-15 株式会社ビックカメラ 発光網戸
JP2002075286A (ja) * 2000-08-24 2002-03-15 Nec Kansai Ltd 平面型発光素子
JP2003053195A (ja) * 2001-08-13 2003-02-25 Tasuke Iwashita 面状発光素子を光源とする光触媒装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003200043A (ja) * 2002-01-04 2003-07-15 Tasuke Iwashita 有機ｅｌ素子または無機ｅｌ素子を用いた有機物質分解装置
JP2004024461A (ja) * 2002-06-25 2004-01-29 Denso Corp 空気浄化装置
WO2004006969A1 (fr) * 2002-07-11 2004-01-22 Sumitomo Electric Industries, Ltd. Semiconducteur poreux et procede de production correspondant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1772187A4 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007217480A (ja) * 2006-02-15 2007-08-30 Sumitomo Electric Ind Ltd 蛍光体、その製造方法及び該蛍光体を含んだ無機ｅｌ素子
JP2009540557A (ja) * 2006-06-07 2009-11-19 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ 光デバイス及び光デバイスを製造する方法
JP2012018798A (ja) * 2010-07-07 2012-01-26 Sharp Corp 面発光素子および浄化装置
JP5022525B1 (ja) * 2011-05-11 2012-09-12 パイオニア株式会社 照明装置
WO2012153407A1 (fr) * 2011-05-11 2012-11-15 パイオニア株式会社 Dispositif d'éclairage
JP2012238575A (ja) * 2012-03-13 2012-12-06 Pioneer Electronic Corp 照明装置
JP2013244440A (ja) * 2012-05-24 2013-12-09 Sharp Corp 水浄化装置
JP2016080347A (ja) * 2014-10-14 2016-05-16 ネプチューン−ベンソン，エルエルシー マルチセグメント型管板
JP2017029923A (ja) * 2015-07-31 2017-02-09 株式会社 シリコンプラス ウイルス除去用フィルター
JP2017221896A (ja) * 2016-06-15 2017-12-21 東芝ライテック株式会社 光触媒装置

Also Published As

Publication number Publication date
US20080274018A1 (en) 2008-11-06
EP1772187A4 (fr) 2013-10-16
EP1772187A1 (fr) 2007-04-11
JPWO2005123246A1 (ja) 2008-04-10
US7767158B2 (en) 2010-08-03
CA2570352A1 (fr) 2005-12-29
JP4743634B2 (ja) 2011-08-10
TW200613045A (en) 2006-05-01

Similar Documents

Publication Publication Date Title
JP4743634B2 (ja) 面発光デバイス
EP1843401A1 (fr) Dispositif d'emission en surface
US8709341B2 (en) System for purifying air through germicidal irradiation and method of manufacture
KR101351485B1 (ko) 섬유필터 및 공기청정기
JP2006237563A (ja) 面発光デバイス
WO2004045756A2 (fr) Appareil et procede de purification et de desinfection photocatalytiques de fluides
US11224860B2 (en) Nanofiber surfaces
TW201030390A (en) Display filter and display device removing indoor air pollutants
US20230234032A1 (en) Filter medium for air and water purification and disinfection
JPH10202110A (ja) フレキシブルな光触媒体
WO2005053363A1 (fr) Fibre el et reacteur de reaction photocatalytique
JP2000167355A (ja) 浄化装置
CN1410151A (zh) 高吸附性光催化空气处理器
US20070126341A1 (en) El fiber and photocatalyst reaction vessel
KR20070022864A (ko) 면발광 디바이스 및 이것을 사용한 여과 필터, 광어시스트형 세라믹 필터
JP2000225349A (ja) フィルター
RU2465046C1 (ru) Композитный адсорбционно-каталитический материал для фотокаталитического окисления
CN1607035A (zh) 废气处理紫外灯制作方法及废气处理方法
JPH11216365A (ja) 光触媒体、光触媒装置及び収容装置
CN209680108U (zh) 一种具有蓄能光电催化型空气净化复合薄膜
JP4174087B2 (ja) 光触媒複合体及び浄水装置
JP2005026275A (ja) 多孔質半導体デバイスとその製造方法
JP2005161267A (ja) 多孔質発光体、ろ過フィルタ並びに浄化装置
JP2006297319A (ja) 脱臭体
RU2751199C1 (ru) Устройство очистки воздуха

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2006514680

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 11628947

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2570352

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2005743654

Country of ref document: EP

Ref document number: 200580019627.0

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Ref document number: DE

WWE Wipo information: entry into national phase

Ref document number: 1020077000810

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1020077000810

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2005743654

Country of ref document: EP